Ice colors of the azole series



United States Patent 2,725,317 I 7 ICE COLORS OF THE AZOLE saunasFrederick Brody, New York, N. Y., and Robert S. Long, Bound Brook, N.5., assignors to American Cyanamid Company, New York, N. Y., acorporation of Maine No Drawing. Original application March 1, 1952,Serial No. 274,490, now PatentNo. 2,695,298, dated November 23, 1954.Divided and this application January 14, 1954, Serial No. 404,127

7 Claims. (Cl. 260-157) This invention relates to compounds of theformula,

in which X is selected from the group of O and S, R is lower alkyl, andR is the residue of an ice-color coupling component.

The production of azoic coloring matters of a greenish shade of blue andsatisfactory fastness properties has been a considerable problem. Suchcoloring mattersare rare and have been both expensive and frequentlypossessed. disadvantageous properties; We have found that azoic coloringmatters in which R in the "above formula is the residue of an arylide of2-hydroxy-3- naphthoic acid are blue azoic coloring matters of very raregreenish shade and have good fastness properties. These constitute thepreferred embodiment of the present invention which, however, is notlimited thereto as a wide range of other shades are obtained whendifferent coupling components are used.

The intermediate amines which are diazotized to form the diazocomponents of the coloring matters of the present invention, that is tosay, compounds having the formula,

in which X is selected from the group of O and S, and R is lower alkyl,are in themselves new compounds. They are, however, not claimed in thepresent application forming the subject matter of a parent case, SerialNo. 274,490, filed March 1, 1952, now Patent No. 2,695,298 of which thepresent application is a division.

It is an advantage of the present invention that the amines diazotizesmoothly and couple readily with icecolor coupling components, such asbeta-naphthol, 8- amino-2 naphthol, 8 acetylamino 2 naphthol, benzylnaphthols, pyrazolones, hydroxybenzofluorenones and the variousN-substituted amides such as arylides of 2- hydroxy-S-naphthoic acid,2-hydroxy-3-anthroic acid, of methyl and dimethyl-salicyclic acids, ofhydroxybenzacridone carboxylic acids, hydroxybenzofuran carboxylicacids, of hydroxybenzothiophene carboxylic acids, of acetoacetic acid,of benzoylacetic acid and the like.

This invention is further illustrated by the following examples. Wherenot otherwise noted, parts are by weight.

A mixture of 2.1'-:-parts. of .2,5-dimethoxy-4-aminoacetanilide, 3.07parts of 2-chlorobenzoxazole and2 parts of N hydrochloric acid in 50parts of 50% dioxa'ne-water is refluxed. Condensation is rapid. Themixture is then cooled, drowned and filtered. The product may becrystallized from ethanol.

Example 2 OHIO A mixture of 8.0 parts'of the product of'Examplel andparts of concentrated hydrochloric'acid in 200 parts of ethanol isrefluxed briefly, drowned, made alkaline with ammonia and filtered. Theproduct may be recrystallized from ethanol. Too long refluxing should beavoided, since it tends to cause rupture of the oxazole ring withformation of 2,5-dimethoxy-p-phenylenediamine.

Example 3 on o 0 H (EONHCsHs N (I CNE S C 2H5 A mixture of 17.0 parts of2-chlorobenzothiazole, 23.8 parts of 2,5-diethoxy-4-aminoacetanilide and10 parts of N hydrochloric acid in 250 parts of 50% dioxane-water isrefluxed until condensation is complete. The mixture is then cooled,drowned in 500 parts of water and filtci'ed. A good yield of product isobtained.

Example 5 N CNH S CaHsO A mixture of 3.71 parts of the product ofExample 4 with 12 parts of concentrated hydrochloric acid and 20 partsof ethanol is refluxed until hydrolysis is complete, drowned in parts ofwater and then made alkaline with sodium hydroxide. On filtration, anexcellent yield NHCOCH:

Paitented Nov- 2. 1

3 of product is obtained; which may be recrystallized from 4. An azoiccoloring matter having the formula ethanol: CUNHOBHi Example 6 l N I VN=N \CNH in which R is lower alkyl and R2 is the residue of an ice colorcoupling component ofthenaphthaleneseries. 6. An azoic coloring matterhaving the formula i m WhlCh X is selectedfi'om the group of O and S, Ris lower alkyl, and R is thewresidue of arrice-color coupling component.of'. the :naphthalene .series. a

2.. Anazoic coloring matter havinglhe formula in WhlCh 10W?! 3 90 7. Anazoic coloring matterhaving' the formula I) QGiHi 0H QONHCflHr in whichR is lower alkyl and Ris the residue of an ice color coupling componentof the-naphthalene series. No references cited;

3. An azoic' coloring matter having the formula OR or; (IJCNHQGHE 40 inwhich R is lower alkyl.

1. AZOIC COLORING MATTERS OF THE FORMULA